On the Lewis-acid-induced addition of allylstannanes to aldehydes: a spectroscopic investigation

Denmark, Scott E.; Wilson, Thomas M.; Willson, Timothy M.

doi:10.1021/ja00211a058

Cited by 99 publications

(35 citation statements)

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“…11 It was therefore of interest to study the 119 tin chemical shifts of the allyltin trichlorides generated by transmetallation of the alkoxypent-2-enylstannanes to see whether they were consistent with co-ordination of the tin by the alkoxy groups. 12,13 Transmetallation of prop-2-enyl(tributyl)-and -(triphenyl)-stannanes 56 and 59 gave prop-2-enyltin trichloride 57 and either tributyltin chloride 58 or triphenyltin chloride 60 with 119 Sn chemical shifts similar to those in the literature, 12,14,15 see Fig. 5.…”

Section: Resultssupporting

confidence: 69%

Concerning the 1,5-stereocontrol in tin(iv) chloride promoted reactions of 4- and 5-alkoxyalk-2-enylstannanes: trapping intermediate allyltin trichlorides using phenyllithium

Hobson

Thomas

2012

Org. Biomol. Chem.

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Transmetallation of the 5-benzyloxy-4-methylpent-2-en-1-yl(tributyl)- and -(triphenyl)stannanes 1 and 8 using tin(iv) chloride generates an allyltin trichloride that reacts with aldehydes to give (Z)-1,5-anti-6-benzyloxy-5-methylhex-3-en-1-ols 2. The allyltin trichloride believed to be the key intermediate in these reactions has been trapped by phenyllithium to give anti-5-benzyloxy-4-methylpent-1-en-3-yl(triphenyl)stannane 9. Transmetallation of this anti-5-benzyloxy-4-methylpent-1-en-3-yl(triphenyl)stannane 9 generated an allyltin trichloride that reacted with aldehydes to give the (Z)-1,5-syn-6-benzyloxy-5-methylhex-3-en-1-ols 23 and was trapped by phenyllithium to give syn-5-benzyloxy-4-methylpent-1-en-3-yl(triphenyl)stannane 24. Similar stereoselectivity was observed for tin(iv) chloride promoted reactions of this syn-5-benzyloxy-4-methylpent-1-en-3-yl(triphenyl)stannane 24 with aldehydes and with phenyllithium. The allyltin trichlorides generated by transmetallation of 4-hydroxy- and 4-benzyloxy-pent-2-enyl(triphenyl)stannanes 34 and 35 were similarly trapped by phenyllithium to give 4-hydroxy- and 4-benzyloxy-pent-1-en-3-ylstannanes 36 and 37 whose configurations were established by correlation with known compounds. This work confirmed the configurations of the intermediate allyltin trichlorides involved in tin(iv) chloride promoted reactions of 4- and 5-alkoxypent-2-enylstannanes with aldehydes and showed that the high levels of remote stereocontrol were due mainly to kinetically controlled transmetallation. A fuller mechanistic scheme is proposed for the reactions in the 5-benzyloxy-4-methylpent-2-enylstannane series together with relevant (119)Sn NMR data.

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Section: Resultssupporting

confidence: 69%

Concerning the 1,5-stereocontrol in tin(iv) chloride promoted reactions of 4- and 5-alkoxyalk-2-enylstannanes: trapping intermediate allyltin trichlorides using phenyllithium

Hobson

Thomas

2012

Org. Biomol. Chem.

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“…with both systems in the presence of PdCl 2 (PhCN) 2 in DMF-d 7 at 25°C, and the results showed largely similar spectra for both cases (Takahara, Masuyama & Kurusu, 1992). Comparison of the product spectra with literature (Denmark, Wilson T & Wilson TM, 1988) also showed numerous similarities, thus allowing the inference of an allyl trichlorotin intermediate (Scheme VIII,5). From these findings, it thus appears that allyl-SnCl 3 must be the actual allylating agent, attacking the carbonyl compound.…”

Section: Characteristics Of Palladium-catalyzed Carbonyl Allylation Wmentioning

confidence: 67%

Palladium-Catalyzed Carbonyl Allylation Reactions Using Tin Chloride: A Mini-Review

Guidote

Baltazar

Yanela

et al. 2018

KIMIKA

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The treatment of allylic alcohols as synthons of carbanions for carbonyl allylation reactions in the presence of a Pd-SnCl2 system has been one of the most interesting and most useful developments demonstrated by Yoshiro Masuyama and co-workers in the field of organic synthesis. The reaction makes use of palladium as an effective catalyst and tin (II) chloride as a low-valent reducing agent which also effectively transforms the allylic group to a nucleophilic group. The organic, as well as organometallic, chemistry of how the transformations occur and how the metals take part in the reaction is of great interest. These could help allow for better optimization of reagents and solvents, for better control of the extent of reaction or yield of desired product, and for possible applications in other reaction systems. This review will focus primarily on the work of Yoshiro Masuyama and various co-workers on carbonyl allylation reactions making use of a Pd-SnCl2 system or substitutes thereof.

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“…For the interpretation we have to take into consideration the fact that the trioxane formation is known to be reversible and distinctively dependent on the solvent [6,9,10] as well as the fact that the equilibrium 3 RCHO Ð (RCHO) 3 is shifted to the left with higher temperatures (for R=H, Et see ref. [11,12]). Thus, in the case of the propionaldehyde (R=Et) the low amount of aldol condensation product formed at 70°C indicates thermal decomposition of the catalyst complex.…”

Section: Resultsmentioning

confidence: 99%

Ruthenium Catalyzed Reactions of Aldehydes: Molecular Structures of Ruthenium Complexes with Aldehyde Ligands

Sorkau

Wagner

Steinborn

et al. 2005

Transition Met Chem

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RuCl(H)(CO)(PPh 3 ) 3 ](2) was found to catalyze, in the presence of H 2 C=CHSiMe 3 (3), the trimerisation of aldehydes RCHO [R=Et (4a), i-Bu (4b)] yielding 1,3,5-trioxanes (5) and the aldol condensation yielding a,b-unsaturated aldehydes (6). When (4a) was used as a reactant, from these reaction mixtures, the ruthenium complex [RuCl 2 (CO)(PPh 3 ) 2 (EtCH@CMeACHO-jO)] (7) having the aldol condensation product as the ligand crystallized. In the analogous reaction with (4b), the complex [RuCl 2 (CO)(PPh 3 ) 2 (i-BuCHO-jO)] (8) with the aldehyde as ligand was obtained. The constitution of these complexes was established by single-crystal X-ray diffraction measurements. The ruthenium centers are octahedrally coordinated having the aldehyde and the carbonyl ligand in mutually trans positions (coordination index: OC-6-12). The aldehydes are monodentately coordinated via the carbonyl oxygen atom (jO). The coordination induced elongations of the C@O double bonds [1.242(4) Å (7), 1.234(4) Å (8)] indicate an activation of the aldehydes. Furthermore, the RuACO bond lengths [1.842(4) Å (7), 1.823(4) Å (8)] exhibit a relatively low trans influence of the aldehyde ligands. The formation of the complexes (7) and (8) give an indication that the Lewis acidity of the ruthenium center is of importance for aldehyde activation in the catalytic process.

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On the Lewis-acid-induced addition of allylstannanes to aldehydes: a spectroscopic investigation

Cited by 99 publications

References 0 publications

Concerning the 1,5-stereocontrol in tin(iv) chloride promoted reactions of 4- and 5-alkoxyalk-2-enylstannanes: trapping intermediate allyltin trichlorides using phenyllithium

Concerning the 1,5-stereocontrol in tin(iv) chloride promoted reactions of 4- and 5-alkoxyalk-2-enylstannanes: trapping intermediate allyltin trichlorides using phenyllithium

Palladium-Catalyzed Carbonyl Allylation Reactions Using Tin Chloride: A Mini-Review

Ruthenium Catalyzed Reactions of Aldehydes: Molecular Structures of Ruthenium Complexes with Aldehyde Ligands

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